Cyclometallated complexes of Pd(II) with heterobidentate P, As and P, N coordinating ligands

• Published in: Journal of organometallic chemistry 2003-01, Vol.665 (1), p.87-94
• Main Authors: Ares, Raquel, López-Torres, Margarita, Fernández, Alberto, Pereira, M.Teresa, Suárez, Antonio, Mosteiro, Roberto, Fernández, Jesús J, Vila, José M
• Format: Article
• Language: English
• Subjects: As ligands; Metallation; P,N ligands; Palladium; Phosphines
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/S0022-328X(02)02066-1

Treatment of the choride-bridged dimer [Pd{4-(COH)C 6H 3C(H)N(Cy) C2, N}(μ-Cl)] 2 ( 1), with Ph 2PCH 2CH 2AsPh 2 (arphos) in 1:1 molar ratio in acetone gave the dinuclear complex [{Pd[4-(COH)C 6H 3C(H)N(Cy) C2, N](Cl)} 2(μ-Ph 2PCH 2CH 2AsPh 2)] ( 2), with the arsinophosphine as a bridging ligand, and in 1:2 molar ratio in the presence of NH 4PF 6 gave the mononuclear compound [Pd{4-(COH)C 6H 3C(H)N(Cy) C2, N}(Ph 2PCH 2CH 2AsPh 2 P, As)][PF 6], ( 3), with the arsinophosphine chelated to the metal center. Reaction of 1 with Ph 2PCH 2CH 2CH 2NH 2 in 1:2 molar ratio in acetone and NH 4PF 6 afforded [Pd{4-(COH)C 6H 3C(H)N(Cy) C2, N}{Ph 2PCH 2CH 2CH 2N(CMe 2) P, N}][PF 6] ( 4), after intermolecular condensation between the aminophosphine and the solvent. Condensation was precluded by treatment in toluene to give the mononuclear compound [Pd{4-(COH)C 6H 3C(H)N(Cy) C2, N}(Ph 2PCH 2CH 2CH 2NH 2 P, N)][PF 6], ( 5). 1H, 31P{ 1H} and 13C{ 1H}-NMR, IR and mass spectral data are given. The crystal structures of compounds 2– 4 have been determined by X-Ray crystallography. Reaction of the chloro-bridged cyclopalladated dimer compound 1 with heterobidentate (P,As; P,N) ligands yields new mono- or dinuclear complexes. In compound 4 the NH 2 moiety undergoes condensation with acetone upon coordination to the metal center.